Agent and method for flame-retardant processing of polyester-based fiber products

ABSTRACT

The invention provides a flame-retardant processing agent capable of imparting durable flame retardance to polyester-based fiber products without using halogen-based flame retardant. The flame-retardant processing agent is obtained by dispersing at least one phosphoric acid amide selected from the group consisting of 1,4-piperazinediyl bis(diarylphosphate), diaryl aminophosphate and aryl diaminophosphate as a flame retardant in a solvent in the presence of a nonionic surfactant or an anionic surfactant.

TECHNICAL FIELD

The present invention relates to flame-retardant processing or treatmentof polyester-based fiber products. More particularly, the inventionrelates to a flame-retardant processing or treating agent capable ofimparting durable flame retardance to polyester-based fiber productswithout using halogen-based flame retardant, to a flame-retardantprocessing method using the same, and to flame-retardant processedpolyester-based fiber products obtained using the same.

BACKGROUND ART

A variety of methods for imparting flame retardance to polyester-basedfiber products by post-processing have been hitherto known. For example,there is known a method of attaching, to polyester-based fiber products,a flame-retardant processing agent which is prepared by dispersing, witha dispersant in water, a halogen-containing compound, typically abrominated cycloalkane such as 1,2,5,6,9,10-hexabromocyclododecane asflame retardant (see, for example, Japanese Examined Patent PublicationNo. 53-8840 (1978)). However, by the method of imparting flameretardance to polyester-based fiber products by attachinghalogen-containing compounds thereto will cause some problems: when suchpolyester-based fiber products burn, harmful halogenated gas is formedand this will exert harmful influence to the environment. Therefore, inrecent years, use of such halogen-containing compounds as flameretardant has been restricted.

Under such circumstances, there have been made attempts to impart flameretardance to polyester-based fiber products by use of halogen-freephosphoric ester as flame retardant instead of those halogen-containingcompounds. As such phosphoric esters, for example, aromaticmonophosphates such as tricresyl phosphate and aromatic diphosphatessuch as resorcinol bis(diphenyl phosphate) are known. However, suchphosphoric esters that have hitherto been known as flame retardant canimpart polyester-based fiber products washing-resistant flameretardance, but are not sufficient in resistance to dry cleaning.

Moreover, even if a polyester-based fiber product is provided with flameretardance by using such a phosphoric ester, the phosphoric estergradually moves to the surface of the polyester-based fiber product withtime. During the movement, a dispersion dye and the like used for thedyeing of the polyester-based fiber product also move together with thephosphoric ester to the surface while being dissolved in the phosphoricester to cause so-called “surface bleeding”. Therefore, there arises aproblem of reduction in color fastness.

The present inventors made study to solve the above-mentioned problemsin the conventional flame-retardant processing of polyester-based fiberproducts. As a result, they found that use of some kind of phosphoricacid amide as flame retardant made it possible to impart durable flameretardance to polyester-based fiber products without usinghalogen-containing flame retardant.

Thus, the present inventors have reached the present invention. It istherefore an object of the present invention to provide aflame-retardant processing agent capable of imparting durable flameretardance to polyester-based fiber products, a flame-retardantprocessing method using the same, and to flame-retardant processedpolyester-based fiber products obtained using the same.

DISCLOSURE OF THE INVENTION

The invention provides a flame-retardant processing agent forpolyester-based fiber products, obtained by dispersing at least onephosphoric acid amide selected from the group consisting of

(A) a 1,4-piperazinediyl bis(diarylphosphate) represented by formula(I):

wherein Ar₁, Ar₂, Ar₃ and Ar₄ independently denote an aryl group,(B) a diaryl aminophosphate represented by formula (II):

wherein Ar₁ and Ar₂ independently denote an aryl group, R₁ and R₂independently denote a hydrogen atom, a lower alkyl group, a cycloalkylgroup, an aryl group, an allyl group or an aralkyl group, or R₁ and R₂may be combined together to form a ring, and(C) an aryl diaminophosphate represented by formula (III):

wherein Ar₁ denotes an aryl group, R₁, R₂, R₃ and R₄ independentlydenote a hydrogen atom, a lower alkyl group, a cycloalkyl group, an arylgroup, an allyl group or an aralkyl group, or R₁ and R₂ may be combinedtogether to form a ring, and R₃ and R₄ may be combined together to forma ring, in a solvent in the presence of at least one surfactant selectedfrom the group consisting of nonionic surfactants and anionicsurfactants.

The invention also provides a method for flame-retardant processing of apolyester-based fiber product, comprising flame-retardant treating apolyester-based fiber product with the above flame-retardant processingagent.

The present invention further provides a flame-retardant polyester-basedfiber product obtained by treating a polyester-based fiber product withthe above-mentioned flame-retardant processing agent.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the “polyester-based fiber products” meanfiber containing at least polyester fiber therein, and yarn, cotton andcloth, such as woven fabric and non-woven fabric, containing such fiber.Preferably, the polyester-based fiber products mean polyester fiber, andyarn, cotton and cloth, such as woven fabric and non-woven fabric,formed of such fiber.

Examples of the polyester-based fiber may include, but are not limitedto, fibers of polyethylene terephthalate, polypropylene terephthalate,polybutylene terephthalate, polyethylene naphthalate, polybutylenenaphthalate, polyethylene terephthalate/isophthalate, polyethyleneterephthalate/5-sodiosulfoisophthalate, polyethyleneterephthalate/polyoxybenzoyl and polybutyleneterephthalate/-isophthalate.

The polyester-based fiber products flame-retardant processed accordingto the invention are suitably employed as seats, seat covers, curtains,wallpaper, ceiling cloth, carpet, stage curtains, protective sheets forconstruction use, tents and sailclothes.

The agent of the invention for use in the flame-retardant processing ofpolyester-type fiber product is obtained by dispersing at least onephosphoric acid amide selected from the group consisting of

(A) a 1,4-piperazinediyl bis(diarylphosphate) represented by formula(I):

wherein Ar₁, Ar₂, Ar₃ and Ar₄ independently denote an aryl group,(B) a diaryl aminophosphate represented by formula (II):

wherein Ar₁ and Ar₂ independently denote an aryl group, R₁ and R₂independently denote a hydrogen atom, a lower alkyl group, a cycloalkylgroup, an aryl group, an allyl group or an aralkyl group, or R₁ and R₂may be combined together to form a ring, and(C) an aryl diaminophosphate represented by formula (III):

wherein Ar₁ denotes an aryl group, R₁, R₂, R₃ and R₄ independentlydenote a hydrogen atom, a lower alkyl group, a cycloalkyl group, an arylgroup, an allyl group or an aralkyl group, or R₁ and R₂ may be combinedtogether to form a ring, and R₃ and R₄ may be combined together to forma ring, in a solvent in the presence of at least one surfactant selectedfrom the group consisting of nonionic surfactants and anionicsurfactants.

In a first phosphoric acid amide represented by formula (I), i.e.,1,4-piperazinediyl bis(diarylphosphate), Ar₁, Ar₂, Ar₃ and Ar₄independently denote an aryl group, preferably aryl groups having 6 to18 carbon atoms. Examples of such aryl groups may include phenyl,naphthyl and biphenyl. In particular, phenyl is preferable. The arylgroups may have one or more, preferably one to three, lower alkyl grouphaving 1 to 4 carbon atoms. Examples of such aryl groups having a loweralkyl group may include a tolyl group, a xylyl group and amethylnaphthyl group.

According to the invention, one of preferred example of the firstphosphoric acid amide is 1,4-piperazinediyl bis(diphenyl-phosphate). Forexample, this 1,4-piperazinediyl bis(diphenyl-phosphate) can be obtainedby reacting diphenyl phosphorochloridate with piperazine in a solvent inthe presence of an amine catalyst as disclosed in Japanese UnexaminedPatent Publication No. 10-175985 (1998).

In the second phosphoric acid amide represented by formula (II), i.e.,diaryl aminophosphate, Ar₁ and Ar₂ independently denote an aryl group,preferably an aryl group having 6 to 18 carbon atoms. Examples of sucharyl groups may include phenyl, naphthyl and biphenyl. In particular,phenyl is preferable. The aryl groups may have one or more, preferablyone to three, lower alkyl group having 1 to 4 carbon atoms. Examples ofsuch aryl groups having a lower alkyl group may include a tolyl group, axylyl group and a methylnaphthyl group.

In the diaryl aminophosphate represented by formula (II), R₁ and R₂independently denote a hydrogen atom, a lower alkyl group, a cycloalkylgroup, an aryl group, an allyl group or an aralkyl group. Alternatively,R₁ and R₂ may be combined to form a ring together with the nitrogen atomattached to the phosphorus atom.

In formula (II), the lower alkyl group is preferably an alkyl grouphaving from 1 to 4 carbon atoms, namely, methyl, ethyl, propyl or butyl.The alkyl groups having three or more carbon atoms may be either linearor branched. Examples of the cycloalkyl group may include cyclopentyl,cyclohexyl and cycloheptyl, with cyclohexyl being preferable. The arylgroup is preferably an aryl group having 6 to 18 carbon atoms. Examplesof such an aryl group may include phenyl, naphthyl and biphenyl, and inparticular, phenyl is preferable. The aryl groups may have one or more,preferably one to three, lower alkyl groups having 1 to 4 carbon atoms.Examples of such aryl groups having a lower alkyl group may include atolyl group, a xylyl group and a methylnaphthyl group. The aralkyl groupis preferably benzyl or phenethyl. These may have on their phenyl groupsone or more, preferably one to three, lower alkyl groups having 1 to 4carbon atoms.

In formula (II), R₁ and R₂ may be combined together to form a ringtogether with the nitrogen atom attached to the phosphorus atom. In thiscase, the ring is generally preferably a six-membered ring. Examples ofsuch a six-membered ring may include piperidyl, piperazinyl andmorpholino.

Accordingly, preferred examples of the second phosphoric acid amide mayinclude amino diphenyl phosphate, methylamino diphenyl phosphate,dimethylamino diphenyl phosphate, ethylamino diphenyl phosphate,diethylamino diphenyl phosphate, propylamino diphenyl phosphate,dipropylamino diphenyl phosphate, octylamino diphenyl phosphate,phosphate of diphenylundecylamine, cyclohexylamino diphenyl phosphate,dicyclohexylamino diphenyl phosphate, allylamino diphenyl phosphate,anilino diphenyl phosphate, di-o-cresylphenylamino phosphate, diphenyl(methylphenylamino) phosphate, diphenyl (ethylphenylamino) phosphate,benzylamino diphenyl phosphate and morpholino diphenyl phosphate.

Such diarylamino phosphates can be obtained by reacting an organic aminecompound with a diaryl phosphorochloridate in an organic solvent in thepresence of an amine catalyst as disclosed in Japanese Unexamined PatentPublication No. 2000-154277.

According to the invention, in particular, in the phosphoric acid amiderepresented by formula (II), Ar₁ and Ar₂ are preferably phenyl or tolyl.It is preferable that one of R₁ and R₂ be a hydrogen atom and the otherbe phenyl or cyclohexyl. Examples of such phosphoric acids may includeanilino diphenyl phosphate, di-o-cresylphenylamino phosphate orcyclohexylamino diphenyl phosphate.

In the third phosphoric acid amide represented by formula (III), i.e.,aryldiamino phosphate, Ar₁ is an aryl group, preferably an aryl grouphaving 6 to 18 carbon atoms. Examples of such aryl groups may includephenyl, naphthyl and biphenyl. In particular, phenyl is preferable. Thearyl groups may have one or more, preferably one to three, lower alkylgroup having one to four carbon atoms. Examples of such aryl groupshaving a lower alkyl group may include a tolyl group, a xylyl group anda methylnaphthyl group.

In the aryldiamino phosphate represented by formula (III), R₁, R₂, R₃and R₄ independently denote a hydrogen atom, a lower alkyl group, acycloalkyl group, an aryl group, an allyl group or an aralkyl group.Alternatively, R₁ and R₂ may be combined together to form a ringtogether with the nitrogen atom attached to the phosphorus atom, and R₃and R₄, likewise, may be combined together to form a ring together withthe nitrogen atom attached to the phosphorus atom.

In formula (III), the lower alkyl group is preferably an alkyl grouphaving from 1 to 4 carbon atoms, namely, methyl, ethyl, propyl or butyl.The alkyl groups having three or more carbon atoms may be either linearor branched. Examples of the cycloalkyl group may include cyclopentyl,cyclohexyl and cycloheptyl, and cyclohexyl is preferable. The aryl groupis preferably an aryl group having 6 to 18 carbon atoms. Examples ofsuch an aryl group may include phenyl, naphthyl and biphenyl, and amongthese phenyl is preferable. The aryl groups may have one or more,preferably one to three, lower alkyl group having 1 to 4 carbon atoms.Examples of such aryl group having a lower alkyl group may include atolyl group, a xylyl group and a methylnaphthyl group. The aralkyl groupis preferably benzyl or phenethyl. These may have on their phenyl groupsa lower alkyl group having 1 to 4 carbon atoms.

Moreover, in formula (III), R₁ and R₂ may be combined together to form aring together with the nitrogen atom attached to the phosphorus atom. Inthis case, the ring is generally preferably a six-membered ring.Examples of such a six-membered ring may include piperidyl, piperazinyland morpholino. R₃ and R₄, likewise, may be combined together to form aring together with the nitrogen atom attached to the phosphorus atom. Inthis case, the ring is generally preferably a six-membered ring.Examples of such a six-membered ring may include piperidyl, piperazinyland morpholino. Either only one of the combination of R₁ and R₂ and thecombination of R₃ and R₄ or both combinations may form a ring.

Accordingly, preferred examples of the third phosphoric acid amide mayinclude diamino phenyl phosphate, aminomethyl amino phenyl phosphate,bis(methylamino) phenyl phosphate, amino ethylamino phenyl phosphate,bis(ethylamino) phenyl phosphate, amino propylamino phenyl phosphate,bis(propylamino) phenyl phosphate, amino octylamino phenyl phosphate,amino undecylamino phenyl phosphate, amino cyclohexylamino phenylphosphate, biscyclohexylamino phenyl phosphate, bisarylamino phenylphosphate, amino anilino phenyl phosphate, dianilino phenyl phosphate,anilino methylamino phenyl phosphate, ethylamino phenylamino phenylphosphate, bisbenzylamino phenyl phosphate and dimorpholino phenylphosphate.

Such aryl diamino phosphates can be obtained by reacting an organicamine compound with an aryl phosphorochloridate in an organic solvent inthe presence of an amine catalyst as disclosed in Japanese UnexaminedPatent Publication No. 2000-154277. Especially, according to theinvention, in the phosphoric acid amide represented by formula (III),preferably employed is one in which Ar₁ is phenyl, one of R₁ and R₂ is ahydrogen atom and the other is phenyl or cyclohexyl. Specific examplesof such a phosphoric acid amide may include biscyclohexylamino phenylphosphate and dianilino phenyl phosphate.

The flame-retardant processing agent for polyester-based fiber productsaccording to the invention is obtained by dispersing a phosphoric acidamide such as those described above as a flame retardant in a solvent inthe presence of a surfactant. Water is generally used as the solvent.However, an organic solvent is also employed, if necessary.

As the surfactant, nonionic surfactants or anionic surfactants may beemployed. Moreover, a nonionic surfactant and an anionic surfactant maybe used in combination.

The flame-retardant processing agent according to the invention ispreferably obtained by mixing the phosphoric acid amide with watertogether with the surfactant, and then milling the phosphoric acid amidinto fine particles by use of a wet mill.

Examples of the nonionic surfactant may include polyoxyalkylene typenonionic surfactants such as alkylene oxide adducts of higher alcohol,alkylene oxide adducts of alkylphenol, alkylene oxide adducts of fattyacid, alkylene oxide adducts of fatty acid ester of polyhydric alcohol,alkylene oxide adducts of higher alkylamine and alkylene oxide adductsof fatty acid amide; and polyhydric alcohol type nonionic surfactantssuch as alkyl glycoxides and saccharide fatty acid esters.

On the other hand, examples of the anionic surfactant may includesulfuric ester salts such as higher alcohol sulfuric ester salts, higheralkyl ether sulfuric ester salts and sulfated fatty acid ester salts;sulfonic acid salts such as alkylbenzenesulfonic acid salts andalkylnaphthalenesulfonic acid salts; and phosphoric ester salts such ashigher alcohol phosphoric ester salts and phosphoric ester salts ofhigher alcohol alkylene oxide adducts.

Examples of the organic solvent may include aromatic hydrocarbons suchas toluene, xylene and alkylnaphthalene; ketones such as acetone andmethyl ethyl ketone; ethers such as dioxane and ethyl cellosolve; amidessuch as dimethylformamide; sulfoxides such as dimethyl sulfoxide; andhalogenated hydrocarbons such as methylene chloride and chloroform.

The surfactants and organic solvents may be used alone. Alternativelytwo or more surfactants or organic solvents may be used in combination,if necessary.

Generally, when fiber products are flame-retardant processed bypost-processing, the particle diameter of the flame retardant to be usedhas an important effect on the flame-retardant performance imparted tothe fiber products. Therefore, the smaller the particle diameter of theframe retardant, the higher the flame-retardant performance to beimparted to fiber products.

According to the invention, the particle diameter of the flame retardantusually ranges from 0.3 to 20 μm, preferably 0.3 to 3 μm so that durableflame-retardant performance can be achieved through a sufficientdispersion of the flame retardant inside polyester-based fiber products.

When the flame-retardant processing agent according to the invention isused in flame-retardant processing of polyester-based fiber products, itusually is used after being diluted in water. When being diluted in sucha manner, the amount of the solid matter (phosphoric acid amide as flameretardant) in the flame-retardant processing agent preferably rangesfrom 1 to 50% by weight. The amount of flame-retardant processing agentattaching to a polyester-based fiber product vary depending on the kindof the fiber product, but usually ranges from 0.05 to 30% by weight,preferably 0.5 to 20% by weight as expressed in the amount of flameretardant (phosphoric acid amide). When the amount of the phosphoricacid amide in a flame-retardant processing agent attaching to apolyester-based fiber product is smaller than 0.05% by weight, it isimpossible to impart sufficient flame retardance to the polyester-basedfiber product. On the other hand, when it exceeds 30% by weight, somedefective conditions will be caused; for example, feeling of fiberproducts after flame-retardant processing will get rough and hard.

The method for providing a polyester-based fiber product with theflame-retardant processing agent of the invention is not particularlylimited. For example, according to one of the methods, theflame-retardant processing agent is attached to the polyester-basedfiber product, and the fiber product is heat-treated at a temperaturefrom 170 to 220° C. so that the fiber product takes in the frameretardant phosphoric acid amide into fibers by exhaustion. In this case,the flame-retardant processing agent can be attached to apolyester-based fiber product by, for example, padding, spraying orcoating. According to another method, for example, the polyester-basedfiber product is immersed in the flame-retardant processing agent in abath, and is treated in the bath at a temperature from 110 to 140° C. sothat the fiber product takes in the frame retardant thereinto byexhaustion.

Unless the performance is affected, the flame-retardant processing agentaccording to the invention may, if necessary, contain surfactants otherthan those described hereinabove as dispersing agent. Moreover,according to the invention, the flame-retardant processing agent may, ifnecessary, contain protective colloid agents for improving storagestability, such as polyvinyl alcohol, methyl cellulose, carboxymethylcellulose or starch, flame-retardant aids for improving the flameretardance of the flame-retardant processing agent, ultravioletabsorbers or antioxidants for improving fastness to light. Furthermore,the flame-retardant processing agent may, if necessary, contain knownflame retardants.

The flame-retardant processing agent according to the invention may beemployed together with other fiber processing agents. Examples of suchfiber processing agents may include fabric softeners, antistatic agents,water/oil repellents, hard finishing agents and feeling regulators.

INDUSTRIAL APPLICABILITY

As described above, the use of the flame-retardant processing agent ofthe invention makes it possible to impart highly-performable and durableflame retardance to various types of polyester-based fiber productswithout polluting the environment.

EXAMPLES

The invention will be described with reference to examples, but theinvention is not limited to these examples. In the followingdescription, the particle size distribution of phosphoric acid amide ina flame-retardant processing agent was measured using a laserdiffraction particle size analyzer SALD-2000J manufactured by ShimadzuCorp. and the median diameter was taken as the average particlediameter.

Example 1 Production of Flame-Retardant Processing Agent A

Into a 2-L separable flask, 600 mL of dichloroethane, 212.3 g oftriethylamine and 139.7 g of aniline were placed. 403.0 g ofdiphenylphosphorochloride was dropped to the mixture over 20 minuteswhile being cooled with water and being stirred. After the completion ofthe dropping, the stirring was continued at a liquid temperature of 60°C. for six hours. The resulting precipitate was collected byfilktration, washed with water, and then dried to yield 383 g of anilinodiphenyl phosphate.

40 parts by weight of this anilino diphenyl phosphate, 3.5 parts byweight of sodium dioctylsulfosuccinate and 0.1 part by weight ofsilicone-based antifoaming agent were mixed with 25 parts by weight ofwater. The mixture was charged in a mill containing glass beads of 0.8mm in diameter and was milled until the phosphoric acid amide had anaverage particle diameter of 0.526 μm. The milled matter was conditionedso that it had a concentration of nonvolatile components of 40% byweight by drying at a temperature of 105° C. for 30 minutes, therebyproviding a flame-retardant processing agent A according to theinvention.

Example 2 Production of Flame-Retardant Processing Agent B

40 parts by weight of the anilino diphenyl phosphate prepared in Example1, 3.5 parts by weight of nonylphenol ethylene oxide 9-mole adduct, 0.5part by weight of sodium dodecyl phenyl ether sulfonate and 0.1 part byweight of silicone-based antifoaming agent were mixed with 25 parts byweight of water. The mixture was charged in a mill containing glassbeads of 0.8 mm in diameter and was milled until the phosphoric acidamide had an average particle diameter of 0.603 μm. The milled matterwas conditioned so that it had a concentration of nonvolatile componentsof 40% by weight by drying at a temperature of 105° C. for 30 minutes,thereby providing a flame-retardant processing agent B according to theinvention.

Example 3 Production of Flame-Retardant Processing Agent C

Into a 2-L separable flask, 200 mL of dichloroethane and 79.3 g ofcyclohexylamine were placed. 42.2 g of phenylphosphorochloride wasdropped to the mixture slowly while cooling with water and stirringAfter the completion of the dropping, the stirring was continued at aliquid temperature of 60° C. for two hours. The resulting precipitatewas collected by filtration, washed with water, and then dried to yield55.8 g of biscyclohexylaminophenyl phosphate.

40 parts by weight of this biscyclohexylaminophenyl phosphate, 3.5 partsby weight of sodium dodecyldiphenyl ether sulfonate and 0.1 part byweight of silicone-based antifoaming agent were mixed with 25 parts byweight of water. The mixture was charged in a mill containing glassbeads of 0.8 mm in diameter and was milled until the phosphoric acidamide had an average particle diameter of 0.556 μm. The milled matterwas conditioned so that it had a concentration of nonvolatile componentsof 40% by weight by drying at a temperature of 105° C. for 30 minutes,thereby providing a flame-retardant processing agent C according to theinvention.

Example 4 Production of Flame-Retardant Processing Agent D

Into a 2-L separable flask, 1000 mL of 1,4-dioxane, 80.8 g oftriethylamine and 34.4 g of piperazine were placed. 214.8 g ofdiphenylphosphorochloride was dropped slowly while cooling with waterand stirring. After the completion of the dropping, the stirring wascontinued at a liquid temperature of 60° C. for four hours. Theresulting reaction mixture was cooled and then transferred into a 5-Lbeaker, to which 3 L of water was then added. The resulting precipitatewas collected by filtration, washed with water, and then dried to yield212 g of 1,4-piperazinediyl bis(diphenylphosphate).

40 parts by weight of this 1,4-piperazinediyl bis(diphenyl-phosphate),3.5 parts by weight of sodium dioctylsulfosuccinate and 0.1 part byweight of silicone-based antifoaming agent were mixed with 25 parts byweight of water. The mixture was charged in a mill containing glassbeads of 0.8 mm in diameter and was milled until the phosphoric acidamide had an average particle diameter of 0.522 μm. The milled matterwas conditioned so that it had a concentration of nonvolatile componentsof 40% by weight by drying at a temperature of 105° C. for 30 minutes,thereby providing a flame-retardant processing agent D according to theinvention.

Example 5 Production of Flame-Retardant Processing Agent E

Into a flask provided with a stirrer, a thermometer, a reflux coolingtube and a dropping funnel, 354 g of triethylamine, 182.5 g ofdiethylamine and 2 L of dichloroethane were placed. Then, 671.5 g ofdiphenylphosphorochloride was dropped over 30 minutes while cooling andstirring so that the internal temperature was kept under 50° C.Thereafter, the stirring was continued at room temperature for threehours. Then, the internal temperature was further raised to 85° C. andstirring was made for another one hour. The resulting reaction mixturewas cooled and the precipitate formed was collected by filtration,washed with water and dried, thereby providing 610 g (yield 80%) ofdiphenyl diethylamino phosphate in the form of white powdery crystalshaving a melting point of 51 to 53° C.

40 parts by weight of the diphenyl diethylamino phosphate, 3.5 parts byweight of sodium dodecyldiphenyl ether sulfonate and 0.1 part by weightof silicone-based antifoaming agent were mixed with 25 parts by weightof water. The mixture was charged in a mill containing glass beads of0.8 mm in diameter and was milled until the phosphoric acid amide had anaverage particle diameter of 0.747 μm. The milled matter was conditionedso that it had a concentration of nonvolatile components of 40% byweight by drying at a temperature of 105° C. for 30 minutes, therebyproviding a flame-retardant processing agent E according to theinvention.

Example 6 Production of Flame-Retardant Processing Agent F

To a dichloroethane (2 L) solution containing 93.1 g of aniline and 120g of triethylamine, 296.7 g of di-o-cresylphosphoryl chloride obtainableby reacting phosphorus oxychloride and o-cresol by a conventional methodwas dropped over three hours while cooling with water and stirring.After the completion of the dropping, the resulting precipitate wascollected by filtration, washed with water and dried, thereby providing282 g (yield 80%) of di-o-cresyl-phenylamino phosphate was obtained inthe form of white powdery crystals having a melting point of 127 to 129°C.

40 parts by weight of the di-o-cresylphenylamino phosphate, 3.5 parts byweight of sodium dioctylsulfosuccinate and 0.1 part by weight ofsilicone-based antifoaming agent were mixed with 25 parts by weight ofwater. The mixture was charged in a mill containing glass beads of 0.5mm in diameter and was milled until the phosphoric acid amide had anaverage particle diameter of 0.339 μm. The milled matter was conditionedso that it had a concentration of nonvolatile components of 40% byweight by drying at a temperature of 105° C. for 30 minutes, therebyproviding a flame-retardant processing agent F according to theinvention.

Example 7 Production of Flame-Retardant Processing Agent G

To a dichloroethane (2 L) solution containing 232.5 g of aniline and252.5 g of triethylamine, 210 g of phenylphosphorochloride obtained byreacting phosphorus oxychloride and phenol in an equivalent molar ratioby a conventional method was dropped over three hours while cooling withwater and stirring. After the completion of the dropping, the resultingprecipitate was collected by filtration, washed with water and dried,thereby providing 237 g (yield 73%) of dianilino phenyl phosphate in theform of white powdery crystals having a melting point of 176 to 178° C.

40 parts by weight of this dianilino phenyl phosphate, 3.5 parts byweight of sodium dodecyldiphenyl ether sulfonate and 0.1 part by weightof silicone-based antifoaming agent were mixed with 25 parts by weightof water. The mixture was charged in a mill containing glass beads of0.8 mm in diameter and was milled until the phosphoric acid amide had anaverage particle diameter of 0.551 μm. The milled matter was conditionedso that it had a concentration of nonvolatile components became 40% byweight by drying at a temperature of 105° C. for 30 minutes, therebyproviding a flame-retardant processing agent G according to theinvention.

Comparative Example 1 Production of Flame-Retardant Processing Agent H

40 parts by weight of frame retardant1,2,5,6,9,10-hexabro-mocyclododecane, 3.5 parts by weight of sodiumdioctylsulfosuccinate and 0.1 part by weight of silicone-basedantifoaming agent were mixed with 25 parts by weight of water. Themixture was charged in a mill containing glass beads of 0.8 mm indiameter and was milled until the flame retardant had an averageparticle diameter of 0.415 μm. The milled matter was conditioned so thatit had a concentration of nonvolatile components of 40% by weight bydrying at a temperature of 105° C. for 30 minutes, thereby providing aflame-retardant processing agent H as a comparative example.

Comparative Example 2 Production of Flame-Retardant Processing Agent I

In 50 parts by weight of water, 40 parts by weight of flame-retardant,tetraphenyl-m-phenylene phosphate, was emulsified and dispersed togetherwith silicone-based antifoaming agent by use of 3.5 parts by weight ofsorbitan monostearate ethylene oxide 20-mole adduct as an emulsifier.The dispersion was conditioned so that it had a concentration ofnonvolatile components of 40% by weight by drying at a temperature of105° C. for 30 minutes, thereby providing a flame-retardant processingagent I as a further comparative example. The flame retardant in theflame-retardant processing agent had an average particle diameter of6.476 μm.

Example 8 and Comparative Example 3

Using the flame-retardant processing agents A to G according to theinvention and the flame-retardant processing agents H and I as thecomparative examples, clothes (Polyester Tropical (weight per unit areaof 140 g/m²) were treated to yield flame-retardant processedpolyester-based fiber products according to the present invention andpolyester-based fiber products as comparative examples. For theseproducts, the results of flame retardant performance tests are shown inTables 1 and 2.

(Test Method)

In each dye bath, 3% owf of dispersion dye, 0.5 g/L of dye dispersant(anionic dispersant) and 15% owf of flame-retardant processing agentaccording to the invention or that as the comparative example werecompounded and the pH was adjusted to 4.6 to 4.8 by acetic acid. Thebath ratio was adjusted to 1:15.

A cloth was put into a dye bath and the bath was heated from 50° C. to130° C. at a rate of 2° C./minute, then held at 130° C. for 60 minutesso that it was treated by exhaustion method in the bath. The cloth wasthen washed with water, dried and subjected to heat treatment at 180° C.for one minute. Thereafter, it was evaluated for flame retardantperformance according to the JIS L 1091 D method (Coil method, when thenumber of flame touches is three or more, the sample is judged aspassing).

(Washing with Water)

Five cycles of treatment were conducted where one cycle was composed,according to JIS K 3371, of washing in water at a bath ratio of 1:40 at60±2° C. for 15 minutes using a weak alkaline class 1 detergent in anamount of 1 g/L, repeating three times a five-minute rinsing at 40±2°C., conducting centrifugal dehydration for two minutes, and then hot airdrying at 60±5° C.

(Dry Cleaning)

For 1 g of sample, six cycles of treatment were conducted where onecycle was composed of cleaning at 30±2° C. for 15 minutes using 12.6 mLof tetrachloroethylene and 0.265 g of charge soap (weight composition ofthe charge soap: nonionic surfactant/anionic surfactant/water=10/10/1).

(Color Fastness)

The test was conducted by the test method for color fastness to water, Bmethod, provided in JIS L 0846. Judgment was made using a gray scale forstain.

(Fastness to Rubbing)

The test was conducted by the test method for color fastness to rubbingprovided in JIS L 0849. Judgement was made using a gray scale for stain.

(Fastness to Light)

According to JIS L 0842, judgement was made using a gray scale forchange in color, at 63° C. after 40 hours and 80 hours.

TABLE 1 Example 8 Flame-retardant processing agent A B C D E Nonvolatilecontent (% by weight) 40 40 40 40 40 Flame retardant content (% byweight) 36.8 36.4 36.8 36.8 36.8 Average particle diameter of flameretardant (μm) 0.526 0.603 0.556 0.522 0.747 Flame-retardant processingAmount of flame-retardant processing agent added (% owf) 15 15 15 15 15Flame retardant-treated cloth Amount of attaching flame retardant (%owf) 2.7 2.1 2.0 2.0 2.3 Feeling Good Good Good Good Good Color fastnessCotton  1 hour Class 5 Class 4 Class 4-5 Class 4-5 Class 4 16 hour Class4-5 Class 4 Class 4 Class 4 Class 4 Polyester  1 hour Class 5 Class 4-5Class 5 Class 5 Class 4 16 hour Class 4 Class 4 Class 4-5 Class 4 Class4 Fastness to rubbing Dry test Class 4 Class 4 Class 4 Class 4 Class 4Wet test Class 4-5 Class 4 Class 4 Class 4 Class 4 Fastness to light(63° C.) 40 hours Class 4-5 Class 4 Class 5 Class 4 Class 4 80 hoursClass 4 Class 4 Class 4-5 Class 4 Class 4 Flame retardant performance(number of flame touches (n = 5)) Initial 4, 5, 5, 4, 4 5, 5, 4, 4, 4 3,4, 4, 4, 4 4, 4, 4, 4, 4 3, 3, 4, 3, 4 After washing 4, 4, 5, 5, 4 5, 5,5, 4, 4 4, 5, 4, 4, 5 5, 4, 4, 5, 5 4, 4, 4, 3, 4 After dry cleaning 5,4, 4, 4, 4 4, 4, 4, 3, 3 3, 4, 4, 4, 4 4, 3, 3, 3, 4 3, 3, 3, 3, 3

TABLE 2 Example 8 Comparative Example 3 Flame-retardant processing agentF G H I Nonvolatile content (% by weight) 40 40 40 40 Flame retardantcontent (% by weight) 36.8 36.8 36.8 36.8 Average particle diameter offlame retardant (μm) 0.339 0.551 0.415 6.476 Flame-retardant processingAmount of flame-retardant processing agent added (% owf) 15 15 15 15Flame retardant-treated cloth Amount of attaching flame retardant (%owf) 2.8 2.1 2.7 4.1 Feeling Good Good Good Slipping Color fastnessCotton  1 hour Class 5 Class 5 Class 4-5 Class 4 16 hour Class 5 Class4-5 Class 4 Class 3 Polyester  1 hour Class 5 Class 5 Class 5 Class 4 16hour Class 4-5 Class 4 Class 4 Class 3-4 Fastness to rubbing Dry testClass 4 Class 4 Class 4 Class 1 Wet test Class 4-5 Class 4-5 Class 4-5Class 1-2 Fastness to light (63° C.) 40 hours Class 4 Class 4 Class 4Class 3 80 hours Class 4 Class 3-4 Class 3 Class 2 Flame retardantperformance (number of flame touches (n = 5)) Initial 5, 5, 4, 4, 4 3,4, 3, 4, 4 5, 4, 4, 4, 4 3, 4, 4, 3, 3 After washing 5, 5, 5, 4, 5 4, 4,5, 4, 3 5, 5, 5, 5, 4 5, 4, 4, 4, 3 After dry cleaning 4, 4, 4, 4, 4 3,4, 3, 3, 4 3, 4, 4, 4, 4 3, 2, 3, 2, 1

Example 9 and Comparative Example 4

A cloth was put, in advance, in a dye bath having a bath ratio of 1:15,3% owf of dispersion dye, 0.5 g/L of dye dispersant (anionic dispersant)and a pH of 4.6 to 4.8 adjusted by acetic acid. The bath was heated from50° C. to 130° C. at a rate of 2° C./minute, then held at 130° C. for 60minutes to subject the cloth to dyeing treatment. The cloth was washedwith water, dried and then subjected to heat treatment at 180° C. forone minute to yield a cloth to be treated.

A flame-retardant processing agent having a solid content of 150 g/L offlame-retardant according to the invention and a flame-retardantprocessing agent having a solid content of 150 g/L of flame-retardant asthe comparative example were prepared. Using each of theseflame-retardant processing agents, the cloth was subjected to paddingtreatment, dried at 100° C. for three minutes, subjected to heattreatment at 180° C. for one minute, and washed with hot water at 80° C.After drying, the cloth was subjected to heat treatment at 180° C. forone minute and then evaluated for flame retardant performance accordingto JIS L 1091, D method. Washing and dry cleaning were conducted in thesame manners as described hereinbefore. The color fastness, fastness torubbing and fastness to light were judged in the same manners asdescribed hereinbefore. The results are shown in Tables 3 and 4.

TABLE 3 Example 9 Flame-retardant processing agent A B C D E Nonvolatilecontent (% by weight) 40 40 40 40 40 Flame retardant content (% byweight) 36.8 36.4 36.8 36.8 36.8 Average particle diameter of flameretardant (μm) 0.526 0.603 0.556 0.522 0.747 Flame-retardant processingAmount of flame-retardant processing agent added (g/L) 150 150 150 150150 Squeezing ratio (% owf) 87.8 84.8 82.8 84.8 83.1 Flameretardant-treated cloth Amount of attaching flame retardant (% owf) 2.32.1 1.9 2.4 2.5 Feeling Good Good Good Good Good Color fastness Cotton 1 hour Class 5 Class 4-5 Class 4-5 Class 4-5 Class 4 16 hour Class 4-5Class 4 Class 4 Class 4 Class 4 Polyester  1 hour Class 4-5 Class 5Class 5 Class 4-5 Class 3-4 16 hour Class 4-5 Class 4 Class 4 Class 4Class 3-4 Fastness to rubbing Dry test Class 4 Class 4 Class 3-4 Class 4Class 3-4 Wet test Class 4 Class 4 Class 4 Class 4 Class 4 Fastness tolight (63° C.) 40 hours Class 4-5 Class 5 Class 4-5 Class 5 Class 4 80hours Class 4 Class 4-5 Class 4 Class 4-5 Class 4 Flame retardantperformance (number of flame touches (n = 5)) Initial 4, 4, 5, 4, 4 5,4, 4, 4, 4 3, 4, 3, 4, 4 4, 4, 4, 4, 4 5, 3, 4, 5, 4 After washing 4, 4,5, 4, 5 5, 5, 5, 4, 5 4, 5, 4, 4, 4 4, 5, 4, 4, 4 4, 4, 4, 4, 4 Afterdry cleaning 3, 3, 3, 3, 4 4, 3, 3, 4, 3 3, 4, 3, 3, 4 3, 4, 3, 3, 3 3,3, 3, 3, 4

TABLE 4 Example 9 Comparative Example 5 Flame-retardant processing agentF G H I Nonvolatile content (% by weight) 40 40 40 40 Flame retardantcontent (% by weight) 36.8 36.8 36.8 36.8 Average particle diameter offlame retardant (μm) 0.339 0.551 0.415 6.476 Flame-retardant processingAmount of flame-retardant processing agent added (g/L) 150 150 150 150Squeezing ratio (% owf) 83.7 83.4 83.8 85.0 Flame retardant-treatedcloth Amount of attaching flame retardant (% owf) 2.4 2.0 2.3 3.3Feeling Good Good Good Slipping Color fastness Cotton  1 hour Class 5Class 4-5 Class 4-5 Class 4 16 hour Class 5 Class 4 Class 4 Class 3-4Polyester  1 hour Class 5 Class 4 Class 5 Class 4 16 hour Class 4-5Class 4 Class 4 Class 3-4 Fastness to rubbing Dry test Class 4 Class 4Class 3-4 Class 1 Wet test Class 4 Class 4 Class 4 Class 1-2 Fastness tolight (63° C.) 40 hours Class 4 Class 4 Class 3-4 Class 5 80 hours Class3-4 Class 3-4 Class 3 Class 4-5 Flame retardant performance (number offlame touches (n = 5)) Initial 5, 4, 4, 5, 4 3, 4, 3, 4, 4 4, 4, 4, 4, 43, 4, 3, 3, 3 After washing 5, 5, 5, 5, 4 4, 3, 3, 4, 3 4, 5, 4, 5, 5 3,3, 3, 4, 3 After dry cleaning 4, 4, 3, 4, 3 3, 3, 4, 4, 3 3, 4, 3, 3, 41, 1, 1, 1, 2

1-6. (canceled)
 7. A method for flame-retardant treatment of apolyester-based fiber product, comprising applying the polyester-basedfiber product with a flame-retardant treating agent obtained by mixing aphosphoric acid amide represented by formula (I):

wherein Ar₁, Ar₂, Ar₃ and Ar₄ independently denote an aryl group, withwater together with at least one surfactant selected from the groupconsisting of nonionic surfactants and anionic surfactants, and thenmilling the phosphoric acid amide into fine particles having a particlediameter in the range of 0.3 to 3 μm, so that the polyester-based fiberproduct has the phosphoric acid amide attached thereto in an amount of0.5 to 20% by weight based on the polyester-based fiber product.
 8. Amethod for flame-retardant treatment of a polyester-based fiber product,comprising applying a flame-retardant treating agent obtained by mixinga phosphoric acid amide represented by formula (I):

wherein Ar₁, Ar₂, Ar₃ and Ar₄ independently denote an aryl group, withwater together with at least one surfactant selected from the groupconsisting of nonionic surfactants and anionic surfactants, and thenmilling the phosphoric acid amide into fine particles having a particlediameter in the range of 0.3 to 3 μm, to the polyester-based fiberproduct, drying the resultant, and heat-treating the resultant at atemperature from 170 to 220° C., so that the polyester-based fiberproduct has the phosphoric acid amide attached thereto in an amount of0.5 to 20% by weight based on the polyester-based fiber.
 9. A method forflame-retardant treatment of a polyester-based fiber product, comprisingtreating the polyester-based fiber product by an exhaustion method inwhich the polyester-based fiber product is immersed in a bath containinga flame-retardant treating agent therein and is heated at a temperaturefrom 110 to 140° C. so that the polyester-based fiber product takes upthe flame-retardant treating agent therein, the flame-retardant treatingagent being obtained by mixing a phosphoric acid amide represented byformula (I):

wherein Ar₁, Ar₂, Ar₃ and Ar₄ independently denote an aryl group, withwater together with at least one surfactant selected from the groupconsisting of nonionic surfactants and anionic surfactants, and thenmilling the phosphoric acid amide into fine particles having a particlediameter in the range of 0.3 to 3 μm, so that the polyester-based fiberproduct has the phosphoric acid amide attached thereto in an amount of0.5 to 20% by weight based on the polyester-based fiber.
 10. The methodaccording to claim 7 wherein the polyester-based fiber product has thephosphoric acid amide attached thereto in an amount of 0.5 to 2.8% byweight based on the polyester-based fiber product.
 11. The methodaccording to claim 8 wherein the polyester-based fiber product has thephosphoric acid amide attached thereto in an amount of 0.5 to 2.8% byweight based on the polyester-based fiber product.
 12. The methodaccording to claim 9 wherein the polyester-based fiber product has thephosphoric acid amide attached thereto in an amount of 0.5 to 2.8% byweight based on the polyester-based fiber product.
 13. The methodaccording to claim 9 wherein the bath further contains a dispersion dyethereby the polyester-based fiber product is dyed and provided with thephosphoric acid amide.
 14. The method according to claim 7 wherein thearyl group is a phenyl group.
 15. The method according to claim 8wherein the aryl group is a phenyl group.
 16. The method according toclaim 9 wherein the aryl group is a phenyl group.